Metal-phthalocyanines containing halo-methyl groups and process of preparing same



atentea Feb. 3, 1948 HALop-Mmm GROUPS .AND 'rimosse oF PREPARING SAME Nemen linten "gn ildock i fand '11claims. (ci. asta-airis) This invention relates'to 'new phthalooyanixe derivatives and more particularly 'itjel'a'tes tb' phthalocyanine derivativesn'eariliggr hlorometliyl or bromomethyl substituents.

l According to the invention we manufacture newV phthalocyanine derivatives by a process which comprises heatinga metal or a. metal-'free substituted or'unsiibstituted'phtiielocyenine with aluminium 'chloride and with syhi-dichlrdimethyl ther or sym-dibnodinethylether, r

inethylfgrous itiis desired toiintro'd a Substance Which in pe'seie of 'aluminium '6h16- ride acts in the same manner V'as does "sym-dichlorodimethyl ether, and preferably in presence of a tertiary amine not itself susceptible of hlero-Or-brOmQ-mihyletien- Asmetal phthalocyanines lwhich may leeftljeated according to the process lf the invention there may be mentioned "for 'example Conner, nickel, iron and aluminiuln'phthalocyanines;copper octa-3 -chlorophthalocyanne, copper'tt'a- 4phenylphthalocyanine and copper tetra-4- benzoylphthalocyanine.

Metal free phthalocyanines'm'ay also be'u's'e'd. The products when these are jused contain aluminium phthalocyanine derivatives.

The tertiary amine which islpreferably'usedfin the -process of the invention is, a s saidsuch that it is not itself susceptible 'of chloro-` 'pr bromo-l methylation; thus it`must rnotcontain benzenoid nuclei or other reactiveigroups -to'tvards chloro; or bromoemethylatln'g agents for ecample "h'ye dr'oxyl groups. Thus for exaniple -triethylaiin oi' pyridine may be used whereas dimethylanilii'l'e or triethanolamine may not.

As a substance which, inthe :presencerofalufn'iinium chloride 'actsinthe vsame manner/als d'O''s sym-dlchlorodimethyl ether there may beu's'ed for. examplevparafonnaldehyde.

'I'he process 4of 'the invention may -be -carried out by mixing together aluminium chloride, the tertiary base and the 'chloor bromo-methylating -agent `and adding `to 'the mixture fthe Tnerfprcdue'ts'ent'inednre-niemyereactwesube stances ana-ineyibetcnusedItoiiemit for example with ftertiryiamiii to figiv'e 'quater'na'y anonce mum salts, *with iinecttns to "'gi've fsulpliiiies, and with 'thioure'ete #give -Eis'irnihiour'cnliim `stilts. They are thus `of f'vlue as intermediates' in'the manufaetureofeyestns'onepigments. Y

The inventiii'iseiuustrtetl'vbiit not 'limiten-by the fcnowing fiexample's 1in which parte fire fb'y Weight.

i s c 2,435,307 phthalocyanine are added to it in portions, the temperature being kept between 55 and 60 C. A deep brown liquid is thus obtained. This liquid is heated at 60129 C." during 60 minutes, andit is then poured into 100 parts of cold water containing 30 parts of concentrated hydrochloric acid, ice being added at intervals in quantities vsuch that the temperature is maintained between 20 Y l v Y 1 and 30 c. The bright Vhhiefs'uspehsioh so .obf L' i' :11 parts 0f anhydrous methylamine are added tained is ltered and the blue solid is Washed free `v t0"30"pa1`ts0f anhydrous alumimum Chlor 1de as from acid with water and nnaiiywashed twiceV described in Example 1- The mlxture is cooled with alcohol. It is then dried at6o c.A ande: .5to 60?` C-and112 parts of sym-dibromodimethyl parts of a bright blue powder are obtained. It ether .are .added-f the temperature being lfept at contains of chlorine and consists substan- 'i' 6")r'70-3`-Vv 5 parte 0f Copper Phthaeeyenme are tially of copper tri(ch1oromethyl) phthalocyanine. 15 then added the temperaturebeng kept PetYVeeP Eamplegz- Y' 55 and 60C. `The resulting brown liquid is and the product is then isolated as described in Example 1. 5.6 parts of a bright blue powder areobtained.` vThis product contains 12.6% chlorine and is amixture ofcopper di(chloromethyl) 5 phthalocyanine andV copper tri(ch1oromethyl) vphthalocyanine Y y Example 6 A mixture of parts of anhydrous aluminium chloride and 10 parts of sym-dichloro-dimethyl ether is heated at 60C. until the aluminium chloride has dissolved and 5 parts of nely powdered copper phthalocyanine are then added in portions to the almost clear melt keeping the tem-V perature between-55 and V60 C. The resulting brown liquid is' heated at 60i2 C. during 60 minutes and it is then drowned into 100 parts of water containing 30 'parts of `concentrated hydrochloric acid, ice being added at intervals in quantitles suiicient to maintaintlie temperature between 20 and 30 C. The bright blue Vsuspen- 30 i.

n methyl) phthalocyamne.

sion is iiltered and the separated'solid is washed acid-free with water, and then itis washed twice with alcohol. `VIt is then dried at 60 C and 5.6l

parts of Ya'bright bluepowder are obtained. This -5 contains 9.1 to 9.5% V.chlorine and consistsjessen-V tiavllyV of copper di(chloromethyl)phthalocyanine.

'y Example 3 The process described in Example 1 is repeated o methyl) phthalocyanine,V

but the final heating is conducted'at 85-90 C. instead of at 60i2 C. The product obtained consists of 7 parts of a dark blue powder containingY 18.2'to 18.5% of chlorine and is essentially copper tetra (chloromethyl) phthalocyanine.

V10 parts of dry pyridine are added to 470V parts of coarsely powdered anhydrous aluminium chlof ride, the temperature being allowed tor risente about 150 C. A clear liquid is Vobtained which;

is cooled to 65 C. and 6.5 parts of sym-dichlorodimethyl ether are added, the. temperature being kept below '70 C. The pale grey mixture iscooled to 5 5 C. and 5 parts ofiinely powdered copper phthalocyanine are added, thetemperature being kept below 60 C. The resulting brownliquid is heated at 60i2 during 60-minutes and the product is then isolated. as described in Example 1. 6.4vparts of a substance containing 18%101 chlorine are obtained in the Vform of a bright blue 60 powder. This consists essentially tetra (chloromethyl) phthalocyanine.

Example 5.

of copper ofrcopperphthalocyanine are addedfthe temper# f5 liarts pyridine fare heated at '75-80f'vr C. during 1 hour. The product is isolated as des'cribed'in Example 1. There is thus obtained 7.3 parts ,of a bright blue powder.

20 It contains 27.1% of bromine and 2.7% of chloy rine and consistssubstantiallyof copper tri bro momethyDphthalocyanine.

' Example? f f In place of the 5 parts of copper phthalocyanine employed in Example 1 there are used'5 parts of nickel phthalocyanine. The vproduct is agreenish-blue powder, containing 13.3% clilo` rine, and'itis a mixtureA of nickel di(chloro methyDphth'alocyanine and nickel tri(chloro^' Example 8 minium. It consists; Yprincipally of tri(chloro Y Example may be obtainedas ldescribed in British patent specication No. 468,043,;and instead of 6.5 parts 0f Sym-dichlor'odmethyl;"ether 3.9 parts of` this substance are used. 5.5 parts of a greenish blue Powder,V containing 12.2%' of'chlorine, are obtained. It consists principally of copper tetra- (chloromethyl)'-tetra-4benzoylphthalocyanine.

Emample Y10 A mme of 10o parts @anhydrous aluminium chloride and 132 parts .of sym-dichlorodimethyl ether is stirred until thev aluminium lchloridehas dissolved and 10 parts of copper tetra-4:-phenyl-v phthalocyanine areadded, keeping the temperaturev between 20 C. and 25. C; The resulting dark grey solution is stirred at-25C.duringj60 minutes. and it isl then poured Vinto a mixture .ei 300 parts ofwater and 99,-'partsof concentrated hydrochloric acid, the` temperature being-"kept 6'5- between 20 YC. and sof/c. byV addition of ice as.

necessary." 'I'he mixture isfltere'd and the-green solid residue is washed rst'with wateruntilit iS. free from acid and then with ethyl alcohol. It is kthen dried at C.- and a bright green powder isi 701 thus obtained. .It contains 22.5%-ofchlorineand consists principally kof f copper .octa-f(chlorometh.

y1)-tetrael-phenylphthalocyanine. i' .x Y

In place ofthe 5' parts of copper phthalocyanine .-wemployed inExample 1, there are used 5 parts 45.01copper.tetraf4fbenzoylphthalocyanine, which anhydrous aluminium chloride and the mixture is heated at 140-150 C. until the aluminium chloride dissolves. The solution is cooled to 65 C. and 13 parts of sym-dichlorodimethyl ether are added thereto. The mixture is then cooled to 50 C. and 5 parts of copper tetra-4thiocyano phthalocyanine are added slowly at 50-53 C. The reaction mixture is stirred at 50-53 C. during minutes and then poured into a mixture of 100 parts of Water and 30 parts of concentrated hydrochloric acid, the temperature being kept between 20 and 30 C. by the addition of ice as necessary. The green suspension is filtered and the separated solid is rst washed with Water until free from acid, and then with ethyl alcohol. It is then dried at 60 C. and 5.5 parts of a dark green powder are obtained. It contains 11.2% of chlorine and consists substantially of copper tri-(chloromethyl) -tetra-4 thiocyanophthalocyanine.

Example 12 The process described in Example 4 is repeated, but the final heating is conducted at 65-67 C. instead of at 60 C. The product obtained is a bright blue powder and contains 23% -of chlorine. It is a mixture of copper penta-(chloromethyl) -phthalocyanine and copper hem-(chloromethyl) phthalocyanine.

Example 13 A mixture of 5.72 parts of copper tetra-4- phenyl-phthalocyanine, 100 parts of nitrobenzene and 22 parts of anhydrous aluminium chloride is stirred for 10-15 minutes. A solution of 6 parts of sym-dichlorodimethyl ether in 25 parts of nitrobenzene is then added to the mixture during 15 minutes at 25-30 C. The mixture is then maintained at 25-30 C. during 3 hours and then parts of 20% aqueous hydrochloric acid are added sufciently slowly so that the temperature does not rise above 30 C. 200 parts of ethyl alcohol are then added, and the mixture is filtered. The residual solid is washed with ethyl alcohol and then with water. It is then boiled with 200 parts of 5% aqueous hydrochloric acid, the resulting mixture is filtered and the residual solid is washed free from vacid with water. It is dried at 60 C. and a bright green powder is obtained. It contains 13% of chlorine and consists principally of copper tetra-(chloromethyl) tetra-4-phenylphthalocyanine.

We claim:

1. A phthalocyanine compound of the general formula Q-(CHZX) n, wherein Q is the radical resulting from the removal of n hydrogen atoms from the phenylene nuclei of a metal-phthalocyanine, X stands for a halogen atom of the group consisting of C1 and Br, and n is a numeral not less than 1.

2. A copper phthalocyanine compound characterized by bearing in at least one of its phenylene nuclei at least one radical selected from the group consisting of CI-IzCl and CHzBr.

3. Tri(chloromethyl) -copper-phthalocyanine.

4. Tetra(chloromethyl) copper phthalocyanine.

5. Copper tetra(chloroznethy1) -tetra-#l-phenylphthalocyanine.

6. Process for the manufacture of phthalocyanine compounds having reactive side chains, which comprises reacting a phthalocyanine compound selected from the group consisting of metal-phthalocyanines and metal-free-phthalocyanines, and having at least one position in at least one of its phenylene nuclei unsubstituted, with a member of the group consisting of symmetrical dichlorodimethyl-ether, symmetrical dibromo-dimethyl-ether and paraformaldehyde, in the presence of aluminum chloride.

7. A process as in claim 6, wherein the reaction is carried out in the further presence of a tertiary nitrogenous base which is free of benzenoid nuclei and free of substituents which are reactive toward chloromethylating agents.

8. Process for the manufacture of a copperphthalocyanine compound having at least one CHzCl radical in at least one of its phenylene nuclei, which comprises reacting a copper-phthalocyanine compound having at least one free position in at least one of its phenylene nuclei, with symmetrical dichloro-dimethyl-ether in the presence of aluminum chloride.

9. A process as in claim 8, the reaction being carried out in the further presence of a nitrogenous tertiary base which is free of benzenoid nuclei and free of substituents which are reactive toward dichloro-dimethyl-ether.

10. A process as in claim 8, the reaction being carried out in the further presence of triethylamine.

11. A process as in claim 8, the reaction being carried out in nitrobenzene.

NORMAN HULTON HADDOCK. CLIFFORD WOOD.

REFERENCES CITED FOREIGN PTENTS Country Date Great Britain Dec. 5, 1938 Number 

